US5147752A - Process for producing electrophotographic light-sensitive material - Google Patents
Process for producing electrophotographic light-sensitive material Download PDFInfo
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- US5147752A US5147752A US07/607,328 US60732890A US5147752A US 5147752 A US5147752 A US 5147752A US 60732890 A US60732890 A US 60732890A US 5147752 A US5147752 A US 5147752A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0589—Macromolecular compounds characterised by specific side-chain substituents or end groups
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/0546—Polymers comprising at least one carboxyl radical, e.g. polyacrylic acid, polycrotonic acid, polymaleic acid; Derivatives thereof, e.g. their esters, salts, anhydrides, nitriles, amides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0528—Macromolecular bonding materials
- G03G5/0592—Macromolecular compounds characterised by their structure or by their chemical properties, e.g. block polymers, reticulated polymers, molecular weight, acidity
Definitions
- the present invention relates to a process for producing an electrophotographic light-sensitive material, and more particularly to a process for producing an electrophotographic light-sensitive material which is excellent in electrostatic characteristics and moisture resistance.
- An electrophotographic light-sensitive material may have various structures depending upon the characteristics required or an electrophotographic process to be employed.
- An electrophotographic system in which the light-sensitive material comprises a support having thereon at least one photoconductive layer and, if necessary, an insulating layer on the surface thereof is widely employed.
- the electrophotographic light-sensitive material comprising a support and at least one photoconductive layer formed thereon is used for the image formation by an ordinary electrophotographic process including electrostatic charging, imagewise exposure, development, and, if desired, transfer.
- a process using an electrophotographic light-sensitive material as an offset master plate precursor for direct plate making is widely practiced.
- a direct electrophotographic lithographic plate has recently become important as a system for printing in the order of from several hundreds to several thousands of prints having a high image quality.
- Binders which are used for forming the photoconductive layer of an electrophotographic light-sensitive material are required to be excellent in the film-forming properties by themselves and to possess the capability of dispersing photoconductive powder therein. Also, the photoconductive layer formed using the binder is required to have satisfactory adhesion to a base material or support. Further, the photoconductive layer formed by using the binder is required to have various excellent electrostatic characteristics such as high charging capacity, small dark decay, large light decay, and less fatigue before light-exposure and also have an excellent image forming properties, and the photoconductive layer stably maintains these electrostatic properties to change of humidity at the time of image formation.
- binder resins for a photoconductive layer which satisfy both the electrostatic characteristics as an electrophotographic light-sensitive material and printing properties as a printing plate precursor are required.
- binder resins used for electrophotographic light-sensitive materials have various problems particularly in electrostatic characteristics such as charging property, dark charge retention, light sensitivity, etc., and smoothness of the photoconductive layer.
- JP-A-63-2173 and JP-A-1-70761 disclose improvements in the smoothness of the photoconductive layer and electrostatic characteristics by using, as a binder resin, a resin having a low molecular weight containing from 0.05 to 10% by weight of a copolymer component containing an acidic group in side chains of the polymer or a resin having a low molecular weight (i.e., a weight average molecular weight (Mw) of from 1 ⁇ 10 3 to 1 ⁇ 10 4 ) having an acidic group bonded at the terminal of the polymer main chain thereby obtaining an image having no background stains.
- a binder resin a resin having a low molecular weight containing from 0.05 to 10% by weight of a copolymer component containing an acidic group in side chains of the polymer or a resin having a low molecular weight (i.e., a weight average molecular weight (Mw) of from 1 ⁇ 10 3 to 1 ⁇ 10 4 ) having an acidic group bonded at the
- JP-A-1-100554 and JP-A-1-214865 disclose a technique using, as a binder resin, a resin containing a polymer component containing an acidic group in side chains of the copolymer or at the terminal of the polymer main chain, and containing a polymer component having a heat- and/or photo-curable functional groups;
- JP-A-1-102573 and JP-A-2-874 disclose a technique using a resin containing an acidic group in side chains of the copolymer or at the terminal of the polymer main chain, and a crosslinking agent in combination;
- JP-A-64-564, JP-A-63-220149, JP-A-63-220148, JP-A-1-280761, JP-A-1-116643 and JP-A-1-169455 disclose a technique using a resin having a low molecular weight (a weight average molecular weight of from 1 ⁇ 10 3 to 1 ⁇ 10 4 ) and a resin having a high molecular weight (
- the film strength of the photoconductive layer can be increased sufficiently and also the mechanical strength of the photosensitive material can be increased without adversely affecting the above-described electrostatic characteristics by using a resin containing an acidic group in side chains or at the terminal of the polymer main chain.
- the present invention has been made for solving the problems of conventional electrophotographic light-sensitive materials as described above and meeting the requirement for the light-sensitive materials.
- An object of the present invention is to provide a process for producing an electrophotographic light-sensitive material having stable and excellent electrostatic characteristics and giving clear good images even when the environmental conditions during the formation of duplicated images are changed to a low-temperature and low-humidity or to high-temperature and high-humidity.
- Another object of the present invention is to provide a process for producing a CPC electrophotographic light-sensitive material having excellent electrostatic characteristics and showing less environmental dependency.
- a further object of the present invention is to provide a process for producing an electrophotographic light-sensitive material effective for a scanning exposure system using a semiconductor laser beam.
- a still further object of this invention is to provide a process for producing an electrophotographic lithographic printing master plate having excellent electrostatic characteristics (in particular, dark charge retentivity and photosensitivity), capable of reproducing faithful duplicated images to original, forming neither overall background stains nor dotted background stains of prints, and showing excellent printing durability.
- electrostatic characteristics in particular, dark charge retentivity and photosensitivity
- an electrophotographic light-sensitive material comprising a support having provided thereon a photoconductive layer containing an inorganic photoconductive substance and a binder resin, which comprises mixing the inorganic photoconductive substance and the binder resin to prepare a dispersion for forming a photoconductive layer, and coating the dispersion on the support, wherein said binder resin contains at least a resin (A) having a weight average molecular weight of from about 1 ⁇ 10 3 to about 1 ⁇ 10 4 , containing a repeating unit represented by formula (I) shown below as a polymer component of said resin, having a crosslinked structure prior to the preparation of said dispersion for forming a photoconductive layer, and having at least one acidic group selected from the group consisting of a --PO 3 H 2 group, a --SO 3 H group, a --COOH group, a ##STR1## group (wherein R represents a hydrocarbon group or a --OR' group (wherein
- the characteristic feature of the electrophotographic light-sensitive material of the present invention resides in that the resin (A) contained in the binder resin previously has a crosslinked structure prior to the preparation of a dispersion of a photoconductive substance for forming a photoconductive layer. That is, as a property of the resin (A) per se used for a binder resin, the polymer thereof is at least partially crosslinked, differing from the crosslinked structure which can be formed in the binder resin after preparation of the dispersion, e.g., in a coating step on a support, a subsequent drying step, etc. of the dispersion.
- the present invention it was found that remarkable improvements can be obtained in electrostatic characteristics (in particular, electrostatic characteristics under severe conditions) and moisture resistance property by using, as a binder resin, a lower molecular weight resin having a previously crosslinked structure and an acidic group bonded to the terminal, as compared with a resin having no crosslinked structure or a resin wherein the crosslinked structure is formed after preparation of the dispersion.
- the difference in the property is considered to occur in dispersing the photoconductive substance in a binder resin, i.e., when the binder resin and the photoconductive substance are mutually reacted. That is, it is considered that the control of the interaction between the photoconductive substance and the binder resin during the dispersion according to the present invention is very effective, and the electrophotographic performance obtained after film formation varies widely depending upon the above control.
- the partially crosslinked structure in the resin (A) can be formed by polymerizing a monomer corresponding to the copolymer component represented by formula (I) above and a polyfunctional monomer containing at least two polymerizable functional groups which are copolymerizable with the above monomer in an amount of not more than about 20% by weight, preferably from 1.0 to 10% by weight, based on the total monomers while appropriately adjusting the polymerization condition so as to form the crosslinked structure.
- the use of the polyfunctional monomer in an amount exceeding 20% by weight based on the total monomers is not preferred due to the decrease in the solubility of the resulting resin in an organic solvent.
- crosslinked structure by intermolecular bonding such as by condensation reaction, addition reaction, etc. sometimes may cause deterioration in electrostatic properties of the resulting electrophotographic light-sensitive material, whereas, the crosslinked structure obtained by the above polymerization is preferred since the electrophotographic light-sensitive material obtained therefrom does not show such deterioration in the electrostatic characteristics.
- polymerizable functional group examples include CH 2 ⁇ CH--, CH 2 ⁇ CH--CH 2 --, ##STR3## CH 2 ⁇ CH--NHCO--, CH 2 ⁇ CH--CH 2 NHCO--, CH 2 ⁇ CH--SO 2 --, CH 2 ⁇ CH--CO--, CH 2 ⁇ CH--O--, and CH 2 CH--S--.
- the monomer having at least two polymerizable functional groups can be those having the same or different functional groups described above.
- the monomer having at least two polymerizable functional groups include monomers having the same polymerizable functional groups, for example, styrene derivatives such as divinylbenzne, trivinylbenzene, etc.; esters of methacrylic acid, acrylic acid or crotonic acid of a polyhydric alcohol (e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols #200, #400, #600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylol propane, trimethylol ethane, pentaerythritol) or a polyhydroxyphenol (e.g., hydroquinone, resorcine, catechol and derivatives thereof), vinyl ethers or allyl ethers; vinyl esters, allyl esters, vinylamides or allylamides of dibasic acids (e.g., malonic acid, succin
- monomers having different polymerizable functional groups include vinyl group-containing ester derivatives and amide derivatives of vinyl group-containing carboxylic acids (e.g., methacrylic acid, acrylic acid, methacryloylacetic acid, acryloylacetic acid, methacryloylpropionic acid, acryloylpropionic acid, itaconyloylacetic acid, itaconyloylpropionic acid, a reaction product between a carboxylic acid anhydride and an alcohol or an amine (e.g., allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid)), for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloylacetate, vinyl methacryloylpropionate, allyl methacryl
- the resin (A) of the present invention is characterized by having a crosslinked structure in at least a part of the polymer, and also the resin (A) should be soluble in an organic solvent used for preparing a dispersion containing at least the inorganic photoconductive substance and the binder resin for forming a photoconductive layer. More specifically, for example, a resin (A) having a solubility of at least 5 parts by weight in 100 parts by weight of toluene at a temperature of 25° C. can be used.
- solvents which can be used for preparing a coating dispersion include halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, methylchloroform and trichlene, alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethers such as tetrahydrofuran and dioxane, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and methyl propionate, glycol ethers such as ethylene glycol monomethyl ether and 2-methoxyethyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, which can be used alone or a mixture thereof.
- the weight average molecular weight of the resin (A) is from about 1 ⁇ 10 3 to about 1 ⁇
- the glass transition point of the resin (A) is preferably from -10° C. to 100° C., and more preferably from 5° C. to 95° C.
- the content of the copolymer component corresponding to the repeating unit of formula (I) in the polymer is preferably 30% by weight or more, more preferably from 50 to 99% by weight.
- R 1 represents a hydrocarbon group which may be substituted, preferably a hydrocarbon group having from 1 to 18 carbon atoms which may be substituted.
- the substituent can be any group other than the above-described acidic group bonded to only one terminal of the polymer main chain, and examples of the substituents include a halogen atom (e.g., fluorine, chlorine and bromine atoms), --O--R 2 , --COO--R 2 , and --OCO--R 2 (wherein R 2 represents an alkyl group having from 1 to 22 carbon atoms, e.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl and octadecyl groups.
- halogen atom e.g., fluorine, chlorine and bromine atoms
- R 2 represents an alkyl group having from 1 to 22 carbon
- Preferred hydrocarbon groups include an alkyl group having from 1 to 18 carbon atoms, which may be substituted (e.g., methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-methoxycarbonylethyl, 2-methoxyethyl, and 3-bromopropyl groups), an alkenyl group having from 4 to 18 carbon atoms, which may be substituted (e.g., 2 -methyl-1-porpenyl, 2-butenyl, 2-pentenyl, 3-methyl-2-pentenyl, 1-pentenyl, 1-hexenyl, 2-hexenyl, and 4-methyl-2-hexcenyl groups), an aralkyl group
- a repeating unit having a hydrocarbon group having from 1 to 5 carbon atoms is preferably contained in an amount of at least 60% by weight in the total units represented by formula (I).
- the repeating unit represented by formula (I) is preferably represented by the following formula (Ia) and/or (Ib): ##STR4## wherein A 1 and A 2 , which may be the same or different, each represents a hydrogen atom, a hydrocarbon group having from 1 to 10 carbon atoms, a chlorine atom, a bromine atom, --COR 3 or --COOR 3 , wherein R 3 represents a hydrocarbon group having from 1 to 10 carbon atoms, and B 1 and B 2 each represents a single bond or a linkage group having 1 to 4 linking atoms connecting between --COO-- and the benzene ring.
- the electrophotographic properties in particular, V 10 , D.R.R., and E 1/10
- the electrophotographic properties are improved and are particularly effective to a light-sensitive material for a scanning exposure system using a semiconductor laser beam.
- polymer molecular chains are suitably arranged in boundary surfaces between photoconductive particles (e.g., zinc oxide) in the light-sensitive layer by the effect of a planner benzene ring having a substituent at the orth-position or a naphthalene ring.
- a 1 and A 2 each preferably represents a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having up to 4 carbon atoms (e.g., methyl, ethyl, propyl, and butyl groups), an aralkyl group having from 7 to 9 carbon atoms (e.g., benzyl, phenethyl, 3-phenylpropyl, chlorobenzyl, dichlorobenzyl, bromobenzyl, methylbenzyl, methoxybenzyl, and chloromethylbenzyl groups), an aryl group (e.g., phenyl, tolyl, xylyl, bromophenyl, methoxyphenyl, chlorophenyl, and dichlorophenyl), or --COR 4 or --COOR 4 , wherein R 4 preferably represents any of the above-recited hydrocarbon groups.
- B 1 is a bond or a linkage group containing 1 to 4 linking atoms which connects between --COO-- and the benzene ring e.g., ##STR5## and --CH 2 CH 2 O--.
- B 2 has the same meaning as B 1 .
- the resin (A) of the present invention preferably contains a functional group capable of curing the resin by the action of at least one of heat and light, i.e., a heat- and/or photo-curable functional group. That is, it is preferred that the resin (A) used in the present invention contains a copolymer component containing a heat- and/or photo-curable functional group, in addition to the functional copolymer component for forming a crosslinked structure in the resin (A) and the copolymer component corresponding to formula (I) (including formulae (Ia) and (Ib)), in order to improve the film strength and thereby to increase the mechanical strength of the electrophotographic light-sensitive material.
- a functional group capable of curing the resin by the action of at least one of heat and light i.e., a heat- and/or photo-curable functional group. That is, it is preferred that the resin (A) used in the present invention contains a copolymer component containing a heat- and/or photo-curable functional
- the proportion of the above-described copolymer component containing a heat- and/or photo-curable functional group in the resin (A) of the present invention is preferably from 1 to 30% by weight, more preferably 5 to 30% by weight.
- the proportion is less than 1% by weight, any appreciable effect on improvement in the film strength of the photoconductive layer is not obtained due to insufficient curing reaction.
- the proportion exceeds 30% by weight, excellent electrophotographic properties are difficult to retain even by the resin (A) of the present invention and are decreased to the same degree as those obtained by conventional resin binders.
- the offset master produced from the resin (A) containing more than 30% by weight of the heat- and/or photo-curable functional group suffers from increased background stains in the non-image area in prints.
- light-curable functional group are those used in conventional photosensitive resins known as photocurable resins as described in Hideo Inui and Gentaro Nagamatsu, Kankosei Kobunshi, Kodansha (1977), Takahiro Tsunoda, Shin-Kankosei Jushi, Insatsu Gakkai Shuppanbu (1981), G.E. Green and B.P. Strak, J. Macro. Sci. Reas. Macro. Chem., C 21(2), pp. 187-273 (1981-1982), and C.G. Rattey, Photopolymerization of Surface Coatings, A Wiley Interscience Pub. (1982).
- the heat-curable functional group includes functional groups excluding the above-specified acidic groups.
- Examples of the heat-curing functional groups are described, e.g., Tsuyoshi Endo, Netsukokasei Kobunshi no Seimitsuka, C.M.C. (1986), Yuji Harasaki, Saishin Binder Gijutsu Binran, Ch. II-I, Sogo Gijutsu Center (1985), Takayuki Ohtsu, Acryl Jushi no Gosei Sekkei to Shin-Yoto, Chubu Kei-ei Kaihatsu Center Shuppanbu (1985), and Eizo Ohmori, Kinosei Acryl Jushi, Techno System (1985).
- curing functional groups are --OH, --SH, --NH 2 --NHR 5 (wherein R 5 represents a hydrocarbon group, such as an alkyl group which may be substituted (e.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, 2-chloroethyl, 2-methoxyethyl, and 2-cyanoethyl group), a cycloalkyl group having from 4 to 8 carbon atoms which may be substituted (e.g., cycloheptyl and cyclohexyl groups), an aralkyl group having from 7 to 12 carbon atoms which may be substituted (e.g., benzyl, phenethyl, 3-phenylpropyl, chlorobenzyl, methylbenzyl, and methoxybenzyl groups) and an aryl group which may be substituted (e.g., phenyl, tolyl,
- T 1 and T 2 each represents --H or --CH 3
- R 12 represents --CH ⁇ CH 2 or --CH 2 CH ⁇ CH 2
- R 13 represents ##STR10## or --CH ⁇ CHCH 3
- R 14 represents --CH 2 CH ⁇ CH 2 or ##STR11##
- R 15 represents --CH ⁇ CH 2 , ##STR12## or --CH ⁇ CHCH 3
- R 16 represents --CH ⁇ CH 2 , ##STR13##
- R 17 represents an alkyl group having 1 to 4 carbon atoms, e represents an integer of from 1 to 11, f represents an integer of from 1 to 10, g represents an integer of 1 to 4, h represents an integer of 2 to 11, Z 1 represents --S-- or --O--, and Z 2 represents --OH or --NH 2 .
- ##STR14 represents --H or --CH 3
- R 12 represents --CH ⁇ CH 2 or --CH 2 CH ⁇ CH 2
- R 13 represents ##STR10## or --CH ⁇ CHCH 3
- R 14 represents --CH 2 CH ⁇ CH 2 or ##STR11
- the resin (A) of the present invention may contain other polymer components in combination with the above-described polymer components, i.e., the polymer component selected from the repeating unit represented by formula (I), (Ia) and/or (Ib), the polymer component for forming the crosslinked structure, and the optional polymer component containing a heat- and/or photo-curable functional group.
- the other polymer components may be any components as long as they are copolymerizable with the above polymer components, and examples of such other components include the repeating unit represented by formula (II): ##STR15## wherein T represents ##STR16## (wherein c and d each represents an integer of 1 or 2, R 7 represents the same group as R 1 in formula (I)); R 1 represents the same group as R 1 in formula (I); and b 1 and b 2 , which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having from 1 to 8 carbon atoms, --COO--R 8 or --COO--R 8 bonded via a hydrocarbon group having from 1 to 8 carbon atoms wherein R 8 represents a hydrocarbon group having from 1 to 18 carbon atoms.
- b 1 and b 2 which may be the same or different, each represents a hydrogen atom, an alkyl group having from 1 to 3 carbon atoms, e.g., methyl, ethyl, and propyl groups), --COO--R 8 or --CH 2 COO--R 8 (wherein R 8 preferably represents an alkyl group having from 1 to 18 carbon atoms or an alkenyl group having from 3 to 18 carbon atoms, e.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, pentenyl, hexenyl, octenyl and decenyl groups, and these alkyl and alkenyl groups may have a substituent as described for the above R 1 .
- styrenes e.g., styrene, vinyltoluene, chlorostyrene, bromostyrene, dichlorostyrene, vinylphenol, methoxystyrene, chloromethylstyrene, methoxymethylstyrene, acetoxystyrene, methoxycarbonylstyrene, and methylcarbamoylstyrene
- acrylonitrile methacrylonitrile, acrolein, methacrolein
- vinyl group-containing heterocyclic compounds e.g., N-vinylpyrrolidone, vinylpyridine, vinylimidazole, and vinylthiophene
- acrylamide and methacrylamide
- the resin (A) used in the binder resin of the present invention is characterized by containing an acidic group selected from the group consisting of a --PO 3 H 2 group, a --SO 3 H group, a --COOH group, ##STR17## group (wherein R represents a hydrocarbon group or a --OR' group (wherein R' represents a hydrocarbon group) and a cyclic acid anhydride-containing group, bonded to only one terminal of the polymer main chain of at least one polymer having the above-described crosslinked structure.
- an acidic group selected from the group consisting of a --PO 3 H 2 group, a --SO 3 H group, a --COOH group, ##STR17## group (wherein R represents a hydrocarbon group or a --OR' group (wherein R' represents a hydrocarbon group) and a cyclic acid anhydride-containing group, bonded to only one terminal of the polymer main chain of at least one polymer having the above-described crosslinked structure.
- the content of the acidic group bonded to the terminal of the polymer main chain is preferably from 0.5 to 15% by weight, and more preferably from 2 to 10% by weight, based on the weight of the resin (A).
- the content of the acidic group in the resin (A) is lower than 0.5% by weight, the initial potential is low and a sufficient image density cannot be obtained.
- the content of the acidic group is higher than 15% by weight, the dispersibility is decreased, and the smoothness of the film and the electrophotographic properties at higher humidity decrease, and, further, the background stains are increased when the electrophotographic light-sensitive material is used as an offset master.
- R represents a hydrocarbon group or a --OR' group (wherein R' represents a hydrocarbon group), and, preferably, R and R' each represents an aliphatic group having from 1 to 22 carbon atoms (e.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, 2-chloroethyl, 2-methoxyethyl, 3-ethoxypropyl, allyl, crotonyl, butenyl, cyclohexyl, benzyl, phenethyl, 3-phenylpropyl, methylbenzyl, chlorobenzyl, fluorobenzyl, and methoxybenzyl groups) and an aryl group which may be substituted (e.g., aryl group which may be substituted (e.g., aryl group which may be substituted) and an aryl
- the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride.
- the cyclic acid anhydride to be contained includes an aliphatic dicarboxylic acid anhydride and an aromatic dicarboxylic acid anhydride.
- aliphatic dicarboxylic acid anhydrides include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-1,2-dicarboxylic acid anhydride ring, cyclohexane-1,2-dicarboxylic acid anhydride ring, cyclohexene-1,2-dicarboxylic acid anhydride ring, and 2,3-bicyclo[2,2,2]octanedicarboxylic acid anhydride.
- These rings may be substituted with, for example, a halogen atom (e.g., chlorine and bromine atoms) and an alkyl group (e.g., methyl, ethyl, butyl, and hexyl groups).
- a halogen atom e.g., chlorine and bromine atoms
- an alkyl group e.g., methyl, ethyl, butyl, and hexyl groups.
- aromatic dicarboxylic acid anhydrides include phthalic anhydride ring, naphtnalenedicarboxylic acid anhydride ring, pyridinedicarboxylic acid anhydride ring and thiophenedicarboxylic acid anhydride ring.
- These rings may be substituted with, for example, a halogen atom (e.g., chlorine and bromine atoms), an alkyl group (e.g., methyl, ethyl, propyl, and butyl groups), a hydroxyl group, a cyano group, a nitro group, and an alkoxycarbonyl group (e.g., methoxycarbonyl and ethoxycarbonyl groups).
- a halogen atom e.g., chlorine and bromine atoms
- an alkyl group e.g., methyl, ethyl, propyl, and butyl groups
- a hydroxyl group e.g., methyl,
- the above described specific acidic group bonded to only one terminal of the polymer chain has either a chemical structure where the acidic group in directly bonded or bonded via a linkage group to one terminal of the polymer main chain.
- the linkage group bonding the acidic group-containing component includes a carbon-carbon bond (single bond or double bond), carbon-hetero atom bond (examples of the hetero atom are oxygen, sulfur, nitrogen, and silicon), and a hetero atom-hetero atom bond, or an optional combination of these atomic groups.
- linkage group examples include a single linkage group selected from ##STR19## (wherein R 21 and R 22 each represents a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, and bromine atoms), a cyano group, a hydroxy group, or an alkyl group (e.g., methyl, ethyl and propyl groups), ##STR20## (wherein R 23 and R 24 each represents a hydrogen atom, a hydrocarbon group having from 1 to 8 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenethyl, phenyl and tolyl groups) or --OR 25 wherein R 25 represents the same hydrocarbon group as described for R 23 .
- R 21 and R 22 each represents a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, and bromine atoms), a
- the resin (A) according to the present invention in which the specific acidic group is bonded to only one terminal of the polymer main chain, can easily be prepared by an ion polymerization process, in which a reagent of various kinds is reacted at the terminal of a living polymer obtained by conventionally known anion polymerization or cation polymerization; a radical polymerization process, in which radical polymerization is performed in the presence of a polymerization initiator and/or a chain transfer agent which contains the specific acidic group in the molecule thereof; or a process in which a polymer having a reactive group at the terminal obtained by the above-described ion polymerization or radical polymerization is subjected to a high molecular reaction to convert the terminal to the specific acidic group.
- the polymer of the resin (A) used in the present invention can be prepared by a method of polymerizing a mixture of a monomer corresponding to the repeating unit represented by formula (I), a polyfunctional monomer for forming the above-described crosslinked structure, other optional monomers, and a chain transfer agent containing an acidic group to be bonded to one terminal, in the presence of a polymerization initiator (e.g., azobis type compounds, peroxides, etc.), a method of polymerizing the above mixture but using a polymerization initiator instead of the chain transfer agent, a method of polymerizing the above mixture except for using a chain transfer agent and a polymerization initiator both containing an acidic group, or any of the above three types of method wherein the polymerization is conducted using a chain transfer agent and/or a polymerization initiator containing an amino group, a halogen atom, an epoxy group, an acid halide group, etc. as a substituent, and then the substituent in the
- chain transfer agent to be used include mercapto compounds containing the acidic group or the reactive group capable of being converted to the acidic group (e.g., thioglycolic acid, thiomalic acid, thiosalicyclic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mecaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-
- the chain transfer agent or the polymerization initiator is usually used in an amount of from about 0.5 to about 15 parts by weight, preferably from 1 to 10 parts by weight, per 100 parts by weight of the total monomers.
- At least one heat- and/or photo-curable resin (B) can be used together with the resin (A) according to the present invention, whereby the film strength of the electrophotographic light-sensitive material can be improved without adversely affecting the properties of the resin (A).
- the resin (B) which can be incorporated into the binder resin in the present invention is a heat- and/or photo-curable resin having a crosslinkable functional group, i.e., a functional group of forming a cross-linkage between polymers by causing a crosslinking reaction by the action of at least one of heat and light, and, preferably a resin which is capable of forming a crosslinked structure by reacting with the above-described functional group which can be contained in the resin (A).
- a crosslinkable functional group i.e., a functional group of forming a cross-linkage between polymers by causing a crosslinking reaction by the action of at least one of heat and light
- the heat-curable functional group include, practically, a group composed of at least one combination of a functional group having a dissociating hydrogen atom (e.g., --OH, --SH, and --NHR 31 (wherein R 31 represents a hydrogen atom, an aliphatic group having from 1 to 12 carbon atoms which may be substituted, and an aryl group which may be substituted) and a functional group selected from ##STR21## --NCO, --NCS, and a cyclic dicarboxylic acid anhydride; --CONHCH 2 OR 32 (R 32 represents a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, and hexyl groups); and a polymerizable double bond group.
- a functional group having a dissociating hydrogen atom e.g., --OH, --SH, and --NHR 31
- R 31 represents a hydrogen atom, an aliphatic group having from 1 to
- the functional group having a dissociating hydrogen atom include, preferably, --OH, --SH, and NHR 31 .
- Examples of the above polymerizable double bond group and the photo-curable functional group are those described above for the heat- and/or photo-curable functional groups contained in the resin (A).
- polyester resins unmodified epoxy resins, polycarbonate resins, vinyl alkanoate resins, modified polyamide resins, phenol resins, modified alkyd resins, melamine resins, acryl resins, and styrene resins and these resins may have the above-described functional group capable of causing a crosslinking reaction in the molecule. It is preferred that these resins do not have the acidic group contained in the resin (A) or have not been modified.
- acrylic acid examples thereof are described in Macromolecular Data Handbook (foundation), edited by Kobunshi Gakkai, published by Baifunkan, 1986.
- Specific examples thereof are acrylic acid, ⁇ - and/or ⁇ -substituted acrylic acids (e.g., ⁇ -acetoxy compound, ⁇ -acetoxymethyl compound, ⁇ -(2-aminomethyl compound, ⁇ -chloro compound, ⁇ -bromo compound, ⁇ -fluoro compound, ⁇ -tributylsilyl compound, ⁇ -cyano compound, ⁇ -chloro compound, ⁇ -bromo compound, ⁇ -chloro- ⁇ -methoxy compound, and ⁇ , ⁇ -dichloro compound), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g., 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-oc
- the resin (B) is a (meth)acrylic copolymer containing a monomer represented by following formula (I) as a copolymer component in an amount of at least 30% by weight.
- the content of the copolymer component having the crosslinkable (crosslinking) functional group in the resin (B) is preferably from 0.5 to 40 mole%.
- the weight average molecular weight of the resin (B) is preferably from about 1 ⁇ 10 3 to about 1 ⁇ 10 5 , and preferably from 5 ⁇ 10 3 to 5 ⁇ 10 4 .
- the compounding ratio of the resin (A) and the resin (B) depends upon the kind and particle sizes of the inorganic photoconductive substance used and the surface state of the desired photoconductive layer, but the ratio of (A):(B) is from 5 to 80:95 to 20 by weight ratio, and preferably from 10 to 50:90 to 50 by weight.
- a crosslinking agent can be used together in order to accelerate the crosslinking in the film.
- organic silane series compounds e.g., silane coupling agents such as vinyltrimethoxysilane, vinyltributoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, and ⁇ -aminopropyltriethoxysilane
- polyisocyanate series compounds e.g., toluylene diisocyanate, cyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polyethylenepolyphenyl isocyanate, hexamethylene diisocyanate, isohorone diisocyanate, and macromolecular polyisocyanate
- polyol series compounds e.g., 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, and 1,1,1-trimethylolpropane
- the amount of the crosslinking agent used in the present invention is from about 0.5 to about 30% by weight, and preferably from 1 to 10% by weight, based on the amount of the resin binder.
- the binder resin may, if necessary, contain a reaction accelerator for accelerating the crosslinking reaction of the photoconductive layer.
- organic acids e.g., acetic acid, propionic acid, butyric acid, benzenesulfonic acid, and p-toluenesulfonic acid
- organic acids e.g., acetic acid, propionic acid, butyric acid, benzenesulfonic acid, and p-toluenesulfonic acid
- polymerization initiators e.g., peroxides and azobis series compounds, preferably azobis series polymerization initiators
- monomers having a polyfunctional polymerizable group e.g., vinyl methacrylate, allyl methacrylate, ethylene glycol diacrylate, divinylsuccinic acid esters, divinyladipic acid esters, diallylsuccinic acid esters, 2-methylvinyl methacrylate, and divinylbenzene
- vinyl methacrylate, allyl methacrylate, ethylene glycol diacrylate, divinylsuccinic acid esters, divinyladipic acid esters, diallylsuccinic acid esters, 2-methylvinyl methacrylate, and divinylbenzene can be used.
- the coating composition containing the binder resin of the present invention for forming a photoconductive layer is coated on a support and is crosslinked or subjected to thermosetting.
- a severer drying condition than that used for producing conventional electrophotographic light-sensitive materials can be employed.
- the drying step is carried out at a higher temperature and/or for a longer time.
- the photoconductive layer may be further subjected to a heat treatment, for example, at from 60° to 120° C. for from 5 to 120 minutes.
- a milder drying condition can be employed.
- the present invention using the resin having a crosslinked structure and the curable resin, it is considered that these resins form an interpenetrating polymer network structure in the photoconductive layer by crosslinking.
- Such a network structure results in a remarkable improvement in the chemical bond density between the resins by the three-dimensional crosslinked structure as compared with the photoconductive layer having a planner crosslinked network structure.
- the film strength is markedly improved, and, when the light-sensitive material is used as a printing plate, the water retention property of the photoconductive layer corresponding to the non-image area is also markedly improved after an oil-desensitization treatment due to the increase in the water-absorption ability by the three-dimensional network structure.
- prints having clear images without background stains can be obtained.
- the binder resin may contain the resin (A) having a weight average molecular weight of from 1 ⁇ 10 3 to 1 ⁇ 10 4 in combination with one of the following resins (C), (D) and (E) each having a high molecular weight (a weight average molecular weight in the range of from 5 ⁇ 10 4 to 5 ⁇ 10 5 ).
- the resin (C) which can be used in the present invention is the resin having a weight average molecular weight of from 5 ⁇ 10 4 to 5 ⁇ 10 5 and containing neither --PO 3 H 2 , --SO 3 H, --COOH and ##STR22## groups (wherein R 3 represents a hydrocarbon group or a --OR 4 group wherein R 4 represents a hydrocarbon group) nor a basic group.
- the resin (D) which can be used in the present invention is the resin having a weight average molecular weight of from 5 ⁇ 10 4 to 5 ⁇ 10 5 and containing from 0.1 to 15% by weight of a copolymer component having at least one functional group selected from a --OH group and a basic group.
- the resin (E) which can be used in the present invention is the resin having a weight average molecular weight of from 5 ⁇ 10 4 to 5 ⁇ 10 5 , and containing either a copolymer component having an acidic group in a content of less than 50% of the content of the acidic group contained in the resin (A) or a copolymer component having at least one acidic group selected from --PO 3 H 2 , --SO 3 H, --COOH and ##STR23## (wherein R 5 represents a hydrocarbon group or a --OR 6 group wherein R 6 represents a hydrocarbon group) having a pKa value larger than that of the acidic group contained in the resin (A).
- the mechanical strength of the photoconductive layer can be improved. That is, the resin (C), (D) and (E) improve the mechanical strength of the photoconductive layer without adversely affecting the high performance in the electrophotographic properties obtained by the resin (A) and also provide a sufficient image forming performance even when the environmental conditions are changed as described above or a laser beam of low output is used.
- the above improvements are considered to be achieved due to that the strength of the interaction between the inorganic photoconductive substance and the binder resins can be suitably changed by using the resin (A) and the resin (C), (D) or (E) having a specific weight average molecular weight, a specific content of the acidic or functional group and a specific position at which the acidic or functional group is bonded.
- the electrophotographic properties and the mechanical strength of the film can be improved markedly due to that the resin (A) having a stronger interaction is selectively and suitably adsorbed on the inorganic photoconductive substance and the resin (C), (D) or (E) having a relatively lower interaction mildly acts on the inorganic photoconductive substance to a degree that the electrophotographic properties are not adversely affected.
- the surface of the photoconductive layer has good smoothness in the case of using as an electrophotographic lithographic printing master plate.
- photoconductive particles such as zinc oxide particles are sufficiently dispersed in the binder resin, when the photoconductive layer is subjected to an oil-desensitizing treatment with an oil-desensitizing solution after imagewise exposure and processing, the non-image portions are sufficiently and uniformly rendered hydrophilic and sticking of a printing ink to the non-image portions at printing is inhibited, whereby no background staining occurs even by printing 10,000 prints.
- the binder resin when the resin (A) and one of the resins (C) to (E) are used together, the binder resin is suitably adsorbed onto inorganic photoconductive particles and suitably coats the particles, whereby the film strength of the photoconductive layer is sufficiently maintained.
- the resin (C) which can be used in the present invention is the resin having a weight average molecular weight of from 5 ⁇ 10 4 to 5 ⁇ 10 5 and having neither the above-described acidic group (i.e., the acidic group at the terminal of the main chain in the resin (A)) nor a basic group at the terminal of the grafted portion and the terminal of the main chain of the copolymer.
- the weight average molecular weight of the resin (C) is preferably from 8 ⁇ 10 4 to 3 ⁇ 10 5 .
- the glass transition point of the resin (C) is in the range of preferably from 0° C. to 120° C., and more preferably from 10° C. to 80° C.
- Any resins (C) which are conventionally used as a binder resin for electrophotographic light-sensitive materials can be used in the present invention alone or as a combination thereof. Examples of these resins are described in Harumi Miyahara and Hidehiko Takei, Imaging, Nos. 8 and 9 to 12, 1978 and Ryuji Kurita and Jiro Ishiwata, Kobunshi (Macromolecule), 17, 278-284 (1968).
- the resin (C) are an olefin polymer, an olefin copolymer, a vinyl chloride copolymer, a vinylidene chloride copolymer, a vinyl alkanoate polymer, a vinyl alkanoate copolymer, an allyl alkanoate polymer, an allyl alkanoate copolymer, styrene, a styrene derivative, a styrene polymer, a styrene copolymer, a butadiene-styrene copolymer, an isoprene-styrene copolymer, a butadiene-unsaturated carboxylic acid ester copolymer an acrylonitrile copolymer, a methacrylonitrile copolymer, an alkyl vinyl ether copolymer, an acrylic acid ester polymer, an acrylic acid ester copolymer, a methacrylic acid
- examples of the resin (C) include (meth)acrylic copolymers or polymers each containing at least one monomer shown by the following formula (III) as a (co)polymer component in a total amount of at least 30% by weight; ##STR24## wherein d 3 represents a hydrogen atom, a halogen atom (e.g., chlorine and bromine atoms), a cyano group, or an alkyl group having from 1 to 4 carbon atoms, and is preferably an alkyl group having from 1 to 4 carbon atoms, and R 31 represents an alkyl group having from 1 to 18 carbon atoms, which may be substituted (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, 2-methoxyethyl, and 2-ethoxyethyl groups), an alken
- R 31 represents preferably an alkyl group having from 1 to 4 carbon atoms, an aralkyl group having from 7 to 14 carbon atoms which may be substituted (particularly, the aralkyl group preferably includes benzyl, phenethyl, naphthylmethyl, and 2-naphthylethyl groups, each of which may be substituted), or a phenethyl group or a naphthyl group which may be substituted (examples of the substituent are chlorine and bromine atoms, methyl, ethyl, propyl, acetyl, methoxycarbonyl, and ethoxycarbonyl groups, and the phenethyl group or naphthyl group may have 2 or 3 substituents).
- a component which is copolymerized with the above-described (meth)acrylic acid ester may be any monomer other than the monomer shown by formula (III), and examples of the monomer are ⁇ -olefins, alkanoic acid vinyl esters, alkanoic acid allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, and heterocyclic vinyls (e.g., 5- to 7-membered heterocyclic rings having from 1 to 3 non-metallicaatoms other than nitrogen atom (e.g., oxygen and sulfur atoms), and practical examples are vinylthiophene, vinyldioxane, and vinylfuran).
- the monomer are ⁇ -olefins, alkanoic acid vinyl esters, alkanoic acid allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, s
- the monomer are alkanoic acid vinyl esters or alkanoic acid allyl esters each having from 1 to 3 carbon atoms, acrylonitile, methacrylonitrile and styrene derivatives (e.g., vinyltoluene, butylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, and ethoxystyrene).
- acrylonitile methacrylonitrile
- the resin (C) used in the present invention does not contain a basic group and examples of such basic groups include an amino group and a nitrogen atom-containing heterocyclic group, which may have a substituent.
- R 3 represents the same group as R 0 .
- the content of the copolymer component containing --OH and/or a basic group is from 0.05 to 15% by weight, and preferably from 0.5 to 10% by weight of the resin (D).
- the weight average molecular weight of the resin (D) is from 5 ⁇ 10 4 to 5 ⁇ 10 5 , and preferably from 8 ⁇ 10 4 to 1 ⁇ 10 5 .
- the glass transition point of the resin (D) is in the range of preferably from 0° C. to 120° C., and preferably from 10° C. to 80° C.
- the OH component or the basic group component in the resin (D) has a weak interaction with the interface with the photoconductive particles and the resin (A) to stabilize the dispersion of the photoconductive particles and improve the film strength of the photoconductive layer after being formed.
- the content of the OH or basic group component in the resin (D) exceeds 15% by weight, the photoconductive layer formed tends to be influenced by moisture, and thus the moisture resistance of the photoconductive layer tend to decrease.
- any conventionally known resins having such properties can be used as the resin (D) in the present invention as long as they have the above-described properties, as described for the resin (C).
- any vinylic compounds each having the substituent (i.e., --OH and/or the basic group) copolymerizable with the monomer shown by aforesaid formula (III) can be used.
- the aforesaid basic group in the resin (D) include, for example, an amino group represented by the following formula (IV) and a nitrogen-containing heterocyclic group: ##STR26## wherein R 41 and R 42 , which may be the same or different, each represents a hydrogen atom, an alkyl group which may be substituted (e.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl, 2-bromoethyl, 2-chloroethyl, 2-hydroxyethyl, and 3-ethoxypropyl groups), an alkenyl group which may be substituted (e.g., allyl, isopropenyl and 4-butynyl groups), an aralkyl group which may be substituted (e.g., benzyl, phenethyl, chlorobenzyl,
- the nitrogen-containing heterocyclic ring as the basic group in the resin (D) include, for example, 5- to 7-membered heterocyclic rings each containing from 1 to 3 nitrogen atoms, and the heterocyclic ring may further contain a condensed ring with a benzene ring, a naphthalene ring, etc. These heterocyclic rings may have a substituent.
- heterocyclic ring examples include pyrrole, imidazole, pyrazole, pyridine, piperazine, pyrimidine, pyridazine, indolizine, indole, 2H-pyrrole, 3H-indole, indazole, purine, morpholine, isoquinoline, phthalazine, naphthyridine, quinoxaline, acridine, phenanthridine, phenazine, pyrrolidine, pyrroline, imidazolidine, imidazoline, pyrazoline, piperidine, piperazine, quinacridine, indoline, 3,3-dimethylindolenine, 3,3-dimethylnaphthindolenine, thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, selenazole, benzoselenazole,
- copolymer component or monomer having --OH and/or the basic group is obtained by incorporating --OH and/or the basic group into the substituent of an ester derivative or amide derivative derived from a carboxylic acid or sulfonic acid having a vinyl group as described in Kobunshi (Macromolecular) Data Handbook (Foundation), edited by Kobunshi Gakkai, published by Baifukan, 1986.
- Such a monomer is 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 3-hydroxy 2-chloromethacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl methacrylate, 10-hydroxydecyl methacrylate, N-(2-hydroxyethyl)acrylamide, N-(3-hydroxypropyl)methacrylamide, N-( ⁇ , ⁇ -dihydroxymethyl)ethylmethacrylamide, N-(4-hydroxybutyl) methacrylamide, N,N-dimethylaminoethyl methacrylate, 2-(N,N-diethylaminoethyl) methacrylate, 3-(N,N-dimethylpropyl) methacrylate, 2-(N,N-dimethylethyl)methacrylamide, hydroxystyrene, hydroxymethylstyrene, N,N-dimethylaminomethylstyrene,
- the resin (D) may contain monomers other than the above-described monomer having --OH and/or the basic group in addition to the latter monomer as a copolymer component.
- monomers are those described above for the monomers which can be used as other copolymer components for the resin (C).
- the weight average molecular weight of the resin (E) is from 5 ⁇ 10 4 to 5 ⁇ 10 5 , and preferably from 7 ⁇ 10 4 to 4 ⁇ 10 5 .
- the acidic group contained in the side chain of the copolymer in the resin (E) is preferably contained in the resin (E) at a proportion of from 0.05 to 3% by weight and more preferably from 0.1 to 1.5% by weight. Also, it is preferred that the acidic group is incorporated in the resin (E) in a combination of the acidic group in the resin (A) shown in Table A below.
- the glass transition point of the resin (E) is preferably in the range of from 0° C. to 120° C., more preferably from 0° C. to 100° C., and most preferably from 10° C. to 80° C.
- the resin (E) shows a very weak interaction on photoconductive particles as compared to the resin (A), has a function of mildly coating the particles, and sufficiently increases the mechanical strength of the photoconductive layer, without adversely affecting the function of the resin (A), when the strength thereof is insufficient by the resin (A) alone.
- the content of the acidic group in the side chain of the resin (E) exceeds 3% by weight, the adsorption of the resin (E) onto photoconductive particles occurs whereby the dispersion of the photoconductive particles is destroyed and aggregates or precipitates are formed, which result in causing a state of not forming coated layer or greatly reducing the electrostatic characteristics of the photoconductive particles even if the coated layer is formed. Also, in such a case, the surface property of the photoconductive layer is roughened thereby reducing the strength to mechanical friction.
- R 5 in ##STR28## of the resin (E) include an alkyl group having from 1 to 12 carbon atoms which may be substituted (e.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, 2-chloroethyl, 2-methoxyethyl, 2-ethoxyethyl, and 3-methoxypropyl groups), an aralkyl group having from 7 to 12 carbon atoms, which may be substituted (e.g., benzyl, phenethyl, chlorobenzyl, methoxybenzyl, and methylbenzyl groups), an alicyclic group having from 5 to 8 carbon atoms, which may be substituted (e.g., cyclopentyl and cyclohexyl groups), and an aryl group which may be substituted (e.g., phenyl, tolyl, xylyl,
- any conventional known resins can be used in the present invention as the resin (E) as long as they have the above-described properties and, for example, the conventionally known resins described above for the resin (C) can be used.
- examples of the resin (E) include a (meth)acrylic copolymer containing the monomer shown by formula (III) described above as the copolymer component in a proportion of at least 30% by weight of the copolymer.
- any acidic group-containing vinyl compounds copolymerizable with the monomer shown by the above formula (III) can be used.
- vinyl compounds are described in Macromolecular Data Handbook (Foundation), edited by Kobunshi Gakkai, Baifukan, 1986.
- vinyl compounds are acrylic acid, ⁇ - and/or ⁇ -substituted acrylic acid (e.g., ⁇ -acetoxy compound, ⁇ -acetoxymethyl compound, ⁇ -(2-amino)methyl compound, ⁇ -chloro compound, ⁇ -bromo compound, ⁇ -fluoro compound, ⁇ -tributylsilyl compound, ⁇ -cyano compound, ⁇ -chloro compound, ⁇ -bromo compound, ⁇ -chloro- ⁇ -methoxy compound, ⁇ , ⁇ -dichloro compound), methacyylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g., 2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, and 4-ethyl-2-octenoic acid), maleic acid, maleic acid half esters, maleic acid
- e represents --H, --CH 3 , --Cl, --Br, --CN, --CH 2 COOCH 3 or --CH 2 COOH
- f represents --H or --CH 3
- n 1 represents an integer of 2 to 18
- m 1 represents an integer of from 1 to 12
- l 1 represents an integer of 1 to 4.
- the resin (E) of the present invention may contain, as a copolymer component, monomers other than the monomer of the formula (III) and the monomer containing the acidic group.
- monomers are those described for the resin (C) as other copolymer components which can be contained in the resin (C).
- the binder resin of the present invention may further contain other resins in addition to the above resin.
- other resins include alkyd resins, polybutyral resins, polyolefins, ethylenevinyl acetate copolymers, styrene resins, styrenebutadiene resins, acrylate-butadiene resins, and vinyl alkanoate resins.
- the content of these other resins should be less than about 30% by weight of the total binder resins since, if the content of other resins exceeds about 30%, the effect (in particular, the improvement of electrostatic characteristics) of the present invention cannot be obtained.
- the compounding ratio of the resin (A) to any of the resins (C) to (E) varies depending upon the type of an inorganic photoconductive substance to be used, the particle sizes of the photoconductive substance, and the surface state thereof, but is generally from 5 to 80/95 to 20 by weight, and preferably from 15 to 60/85 to 40 by weight.
- the ratio of the weight average molecular weight of the resin (C), (D), or (E) to that of the resin (A) is preferably 1.2 or more, and more preferably 2.0 or more.
- the inorganic photoconductive substance used in the present invention include zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, lead sulfide, etc. Of these substances, zinc oxide is particularly preferred.
- the total proportion of the binder resins for the photoconductive layer in the present invention is from 10 to 100 parts by weight, and preferably from 15 to 50 parts by weight per 100 parts by weight of the photoconductive substance.
- various kinds of dyes can be used, if necessary, for the photoconductive layers as spectral sensitizers.
- these dyes are carbonium series dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene series dyes, phthalein series dyes, polymethine dyes (e.g., oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, and styryl dyes), and phthalocyanine dyes (inclusive of metallized dyes) described in Harumi Miyamoto and Hidehiko Takei, Imaging, 1973, (No. 8), page 12, C.J.
- Suitable carbonium series dyes triphenylmethane dyes, xanthene series dyes, and phthalein series dyes are described in JP-B-51-452, JP-A-50-90334, JP-A-50-114227, JP-A-53-39310, JP-A-53-82353, and JP-A-57-16455, and U.S. Pat. Nos. 3,052,540 and 4,054,450.
- polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes, and rhodacyanine dyes which can be used are described in F.M. Harmmer, The Cyanine Dyes and Related Compounds, and specific examples thereof include the dyes disclosed in U.S. Pat. Nos. 3,047,384, 3,110,591, 3,212,008, 3,125,447, 3,128,179, 3,132,942, and 3,622,317, British Patents 1,226,892, 1,309,274, and 1,405,898, and JP-B-48-7814 and JP-B-55-18892. (The term "JP-B" as used herein means an "examined Japanese patent publication”.)
- polymethine dyes capable of spectrally sensitizing in the wavelength region of from near infrared to infrared longer than 700 nm are described in JP-B-51-41061, JP-A-47-840, JP-A-47-44180, JP-A-49-5034, JP-A-49-45122, JP-A-57-46245, JP-A-56-35141, JP-A-57-157254, JP-A-61-26044, and JP-A-61-27551, U.S. Pat. Nos. 3,619,154 and 4,175,956, and Research Disclosure, 216, 117 to 118 (1982).
- the light-sensitive material of the present invention is excellent in that, even when various sensitizing dyes are used for the photoconductive layer, the performance thereof is reluctant to vary by such sensitizing dyes.
- the photoconductive layers may further contain various additives commonly employed in electrophotographic photoconductive layers, such as chemical sensitizers.
- additives are electron-acceptive compounds (e.g., halogen, benzoquinone, chloranil, acid anhydrides, and organic carboxylic acids) described in Imaging, 1973, (No. 8), page 12, and polyarylalkane compounds, hindered phenol compounds, and p-phenylenediamine compounds described in Hiroshi Kokado, Recent Photoconductive Materials and Development and Practical Use of Light-sensitive Materials, Chapters 4 to 6, published by Nippon Kagaku Joho K.K., 1986.
- the amount of these additives is usually from 0.0001 to 2.0 parts by weight per 100 parts by weight of the photoconductive substance.
- the thickness of the photoconductive layer is from 1 ⁇ m to 100 ⁇ m, and preferably from 10 ⁇ m to 50 ⁇ m.
- the thickness of the charge generating layer is from 0.01 ⁇ m to 1 ⁇ m, and preferably from 0.05 ⁇ m to 0.5 ⁇ m.
- an insulating layer can be formed on the photoconductive layer for the protection of the photoconductive layer and for the improvement of the durability and the dark decay characteristics of the photoconductive layer.
- the thickness of the insulating layer is relatively thin but, when the light-sensitive material is used for a specific electrophotographic process, the insulating layer having a relatively thick thickness is formed.
- the thickness of the insulating layer is from 5 ⁇ m to 70 ⁇ m, and particularly from 10 ⁇ m to 50 ⁇ m.
- Charge transporting materials which are used for the double layer type light-sensitive material include polyvinylcarbazole, oxazole series dyes, pyrazoline series dyes, and triphenylmethane series dyes.
- the thickness of the charge transfer layer is from 5 ⁇ m to 40 ⁇ m, and preferably from 10 ⁇ m to 30 ⁇ m.
- Resins which can be used for the insulating layer and the charge transfer layer typically include thermoplastic and thermosetting resins such as polystyrene resins, polyester resins, cellulose resins, polyether resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, polyacryl resins, polyolefin resins, urethane resins, epoxy resins, melamine resins, and silicone resins.
- thermoplastic and thermosetting resins such as polystyrene resins, polyester resins, cellulose resins, polyether resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, polyacryl resins, polyolefin resins, urethane resins, epoxy resins, melamine resins, and silicone resins.
- the photoconductive layer of the present invention can be formed on a conventional support.
- the support for the electrophotographic light-sensitive material is preferably electroconductive.
- the conductive support there are base materials such as metals, papers, plastic sheets, etc., rendered electroconductive by the impregnation of a low resistance material, the base materials in which the back surface thereof (the surface opposite to the surface of forming a photoconductive layer) is rendered electroconductive and having coated with one or more layer for preventing the occurrence of curling of the support, the aforesaid support having formed on the surface a water resistance adhesive layer, the aforesaid layer having formed on the surface at least one precoat, and a support formed by laminating thereon a plastic film rendered electroconductive by vapor depositing thereon an aluminum, etc.
- an inorganic photoconductive substance, a binder resin containing at least the resin (A) defined above, an appropriate solvent, and, optionally, various additives generally used in electrophotographic light-sensitive materials such as sensitizing agent, etc. are mixed in a usual manner to prepare a dispersion for forming a photoconductive layer, the resulting dispersion is then coated on an electroconductive support directly or through appropriate layer(s) such as an intermediate layer or a subbing layer by a conventional coating method such as a wire bar coating method, and the coated layer is dried to obtain an electrophotographic light-sensitive material.
- a mixed solution of 95 g of ethyl methacrylate, 5 g of thioglycolic acid, 2 g of divinylbenzene and 200 g of toluene was heated to 75° C. with stirring under nitrogen gas stream and, after adding thereto 1.5 g of azobisisobutyronitrile (A.I.B.N.), the reaction was carried out for 4 hours. Then, 0.8 g of A.I.B.N. was added to the reaction mixture, followed by reaction for 3 hours and, thereafter, 0.5 g of A.I.B.N. was added thereto, followed by reacting for 3 hours.
- the resulting copolymer had a weight average molecular weight (Mw, hereinafter the same) was 8.3 ⁇ 10 3 .
- a mixed solution of 95 g of benzyl methacrylate, 1.5 g of ethylene glycol dimethacrylate, 1.0 g of n-dodecylmercaptan, 150 g of toluene and 50 g of isopropyl methacrylate was heated to 85° C. under a nitrogen stream.
- 5.0 g of 4,4'-azobis(4-cyanovaleric acid) (A.C.V.) was added while stirring, and the mixture was reacted for 5 hours.
- 1 g of A.C.V. was added thereto, and the mixture was reacted for 4 hours.
- the resulting copolymer had a Mw of 7.5 ⁇ 10 3 .
- each of the copolymers was prepared in the same manner as described in Production Example 1 of Resin (A), except for using the compounds shown in Table 1 below instead of ethyl methacrylate, thioglycolic acid, and divinylbenzene, respectively, in the amounts shown in Table 1.
- Each of the resulting copolymer had a Mw in the range of from 5 ⁇ 10 3 to 9 ⁇ 10 3 .
- a mixed solution of 95 g of 2-chlorophenyl methacrylate, 5 g of 2-mercaptoethanol, 2.3 g of divinylbenzene and 200 g of toluene was heated to 75° C. under a nitrogen stream. While stirring, 2 g of azobis(isovaleronitrile) (A.I.V.N.) was added thereto, and the mixture was reacted for 4 hours, and then 0.8 g of A.I.V.N. was added thereto, and the mixture was reacted for 3 hours. Further, 0.8 g of A.I.V.N. was added thereto, followed by reacting for 3 hours.
- A.I.V.N. azobis(isovaleronitrile)
- a mixture of 40 g (as solid content) of the resin (A-1) produced in Production Example 1 of Resin (A), 200 g of zinc oxide, 0.02 g of a heptamethine cyanine dye (A) having the structure shown below, 0.02 g of phthalic anhydride, and 300 g of toluene was dispersed in a ball mill for 3 hours to prepare a coating composition for a photoconductive layer.
- the composition was coated on a paper, which had been subjected to an electroconductive treatment, by a wire bar in a dry coated amount of 22 g/m 2 and dried for 1 minute at 110° C.
- the coated product was allowed to stand in the dark for 24 hours under conditions of 20° C., 65% RH to obtain an electrophotographic light-sensitive material.
- An electrophotographic light-sensitive material was prepared in the same manner as Example 1, except that 40 g (as solid content) of Resin (A-6) was used in place of the resin (A-1).
- An electrophotographic light-sensitive material was prepared in the same manner as Example 1, except that 40 g of an ethyl methacrylate/acrylic acid (95/5 weight ratio) copolymer (R-1) having a Mw of 8.5 ⁇ 10 3 was used instead of the Resin (A-1).
- An electrophotographic light-sensitive material was prepared in the same manner as Example 1, except that 40 g of the Resin (R-3) having the following structure formula was used in place of the Resin (A-1). ##STR34##
- Each light-sensitive material was charged by applying thereto corona discharging of -6 kV for 20 seconds using a paper analyzer (Paper Analyzer Type SP-428, manufactured by Kawaguchi Denki K.K.) in the dark at 20° C., 65% RH and then allowed to stand for 10 seconds.
- the surface potential V 10 in this case was measured.
- the sample was allowed to stand for 90 seconds in the dark and then the potential V 100 was measured.
- the dark decay retention [DRR (%)] i.e., the percent retention of potential after decaying for 120 seconds in the dark, was calculated from the following formula:
- the surface of the photoconductive layer was charged to -400 volts by corona discharging, then irradiated by monochromatic light of a wavelength of 780 n.m., the time required for decaying the surface potential V 10 to 1/10 thereof, and the exposure amount E 1/10 (erg/cm 2 ) was calculated therefrom.
- Each light-sensitive material was allowed to stand a whole day and night under the environmental condition (I) of 20° C., 65% RH or the environmental condition (II) of 30° C., 80% RH. Then, each sample was charged to -5 kV, exposed by scanning with a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 n.m.) of 2.8 mW in output as a light source at an exposure amount on the surface of 64 erg/cm 2 , at a pitch of 25 m, and a scanning speed of 300 m/sec., and developed using ELP-T (trade name, made by Fuji Photo Film Co., Ltd.) as a liquid developer followed by fixing. Then, the reproduced images (fog, image quality) were visually evaluated.
- ELP-T trade name, made by Fuji Photo Film Co., Ltd.
- the light-sensitive material of the present invention was excellent in electrostatic characteristics as well as the reproduced images formed by processing had no background stains and had clear image quality.
- the resin (A) containing a methacrylate component having a specific substituent (Example 2) has an improved electrostatic characteristics over the resin of Example 1 and is more preferred particularly as a light-sensitive material for the scanning exposure system using a semiconductor laser beam.
- the resulting dispersion was coated on a paper, which had been subjected to an electroconductive treatment, by a wire bar at a dry coated amount of 22 g/m 2 , dried for 30 seconds at 100° C. and then heated for 1 hour at 120° C. Then, the coated product was allowed to stand for 24 hours under the condition of 20° C., 65% RH to obtain an electrophotographic light-sensitive material.
- An electrophotographic light-sensitive material was prepared in the same manner as Example 3, except that 10 g of the resin (R-4) having the following formula was used in place of 10 g of the resin (A-19). ##STR36##
- the coating property surface smoothness
- film strength film strength
- electrostatic characteristics image forming performance under atmospheric condition
- image forming performance under the environmental condition of 30° C., 80% RH were determined.
- each sample was used as an offset master plate after processing, and the desensitizing property of the photoconductive layer (shown by the contact angle between oil-desensitized photoconductive layer and water) and the printing properties (background stains, printing durability, etc.) were determined.
- the smoothness (sec/cc) of each light-sensitive material was measured using a Beck Smoothness Test Machine (manufactured by Komagaya Riko K.K.) under an air volume of 1 cc.
- Each light-sensitive material was charged by applying thereto corona discharging of -6 kV for 20 seconds using a paper analyzer (Paper Analyzer Type SP-428, manufactured by Kawaguchi Denki K.K.) in the dark at 20° C., 65% RH and then allowed to stand for 10 seconds.
- the surface potential V 10 in this case was measured.
- the sample was allowed to stand for 120 seconds in the dark and then the potential V 130 was measured.
- the dark decay retention [DRR (%)] i.e., the percent retention of potential after decaying for 120 seconds in the dark, was calculated from the following formula:
- the surface of the photoconductive layer was charged to -400 volts by corona discharging, then irradiated by monochromatic light of a wavelength of 780 n.m., the time required for decaying the surface potential V 10 to 1/10 thereof, and the exposure amount E 1/10 (erg/cm 2 ) was calculated therefrom.
- Each light-sensitive material was allowed to stand a whole day and night under the environmental condition (I) of 20° C., 65% RH or the environmental condition (II) of 30° C., 80% RH. Then, each sample was charged to -5 kV, exposed by scanning with a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 n.m.) of 2.8 mW in output as a light source at an exposure amount on the surface of 56 erg/cm 2 , at a pitch of 25 ⁇ m, and a scanning speed of 280 m/sec., and developed using ELP-T (trade name, made by Fuji Photo Film Co., Ltd.) as a liquid developer followed by fixing. Then, the reproduced images (fog, image quality) were visually evaluated.
- ELP-T trade name, made by Fuji Photo Film Co., Ltd.
- Each light-sensitive material was passed once through an etching processor using a solution prepared by diluting a oil-desensitizing solution ELP-E (trade name, made by Fuji Photo Film Co., Ltd.) two-times with distilled water to desensitized the surface of the photoconductive layer. Then, one drop of distilled water (2 ⁇ l) was placed on the surface, and the contact angle between the surface and the water drop formed thereon was measured using a goniometer.
- ELP-E oil-desensitizing solution
- Each light-sensitive material was processed in the same manner as described in *5), the sample was oil-desensitized under the dame condition as in *6) described above, and the printing plate thus prepared was mounted on an offset printing machine (Oliver Model 52, manufactured by Sakurai Seisakusho K.K.) as an offset master plate following by printing. Then, the number of prints obtained without causing background staining on the non-imaged portions of prints and problems on the quality of the imaged portions was employed as the printing durability. The larger the number of prints, the higher the printing durability.
- the light-sensitive material of the present invention was excellent in the smoothness of the photoconductive layer, the mechanical strength of the film, and electrostatic characteristics, and the reproduced images formed by processing had no background stains and had clear image quality.
- the binder resin suitably adsorbed on the photoconductive particles and suitably covered the surface of the particles as well as did not hinder the adsorption of spectral sensitizing dyes onto the particles.
- the photoconductive layer was sufficiently oil-desensitized by an oil-desensitizing solution for the same reason as above, and the contact angle between the non-image area and water was as low as below 15 degrees, which showed that the layer was sufficiently rendered hydrophilic. At printing, no background staining of prints was observed.
- the photoconductive layer was sufficiently oil-desensitized by an oil-desensitizing solution, and the content angle between the non-image area and water was as low as below 10 degrees, which showed that the layer was sufficiently rendered hydrophilic.
- the maximum number of prints was about 3,000, and cut of letter or fine lines were generated.
- the dispersion was coated on a paper, which had been subjected to an electroconductive treatment, by a wire bar in a dry coating amount of 22 g/m 2 and dried for 15 seconds at 100° C. and then for 2 hours at 120° C. Then, the coated product was allowed to stand for 24 hours under the condition of 20° C., 65% RH to obtain an electrophotographic light-sensitive material.
- Each of electrophotographic light-sensitive materials was prepared in the same manner as Example 3, except that the resins and the crosslinking agent shown in Table 5 below were used in place of 10 g of the resin (A-19), 30 g of the resin (B-1) and 4 g of glutaconic acid as a crosslinking agent, and that 0.02 g of the cyanine (D) having the following structure was used in place of the cyanine dye (B). ##STR38##
- the light-sensitive materials of the present invention were excellent in the charging property, the dark charge retentivity and the light sensitivity, and the reproduced images formed by processing showed clear images having no background stains and cut of fine lines.
- the light-sensitive material was used as an offset master plate after processing, more than 8,000 prints having clear images without background stains could be obtained on printing.
- the dispersion was added 12 g of the resin (B) in Group Y shown in Table 5, and the mixture was further dispersed in a ball mill for 10 minutes.
- the dispersion was coated on a paper, which had been subjected to an electroconductive treatment, by a wire bar in a dry coating amount of 20 g/m 2 and dried for 15 seconds at 100° C. and then heated for 2 hours at 120° C. Then, the coated material was allowed to stand for 24 hours under the conditions of 20° C, 65% RH to obtain each of electrophotographic light-sensitive materials.
- Each of the light-sensitive materials was excellent in the charging property, dark charge retentivity, and light sensitivity and provided clear images having no background fog under severe conditions of 30° C., 80% RH at practical image formation.
- the light-sensitive material was used for printing as an offset master plate after processing, 8,000 prints having clear images were obtained.
- a mixture of 10 g of the resin (A-5), 18 g of the resin (B-15) having the following formula, 200 g of zinc oxide, 0.50 g of Rose Bengal, 0.25 g of tetrabromophenol blue, 0.30 g of uranine, 0.30 g of tetrahydrophthalic anhydride and 240 g of toluene was dispersed in a ball mill for 2 hours.
- the dispersion was coated on a paper, which had been subjected to an electroconductive treatment, by a wire bar in a dry coating amount of 20 g/m 2 , dried for 30 seconds at 110° C. and then heated for 2 hours at 120° C.
- the coated product was allowed to stand for 24 hours in the dark under conditions of 20° C., 65% RH to obtain an electrophotographic light-sensitive material.
- Each light-sensitive material was charged by applying thereto corona discharging of -6 kV for 20 seconds using a paper analyzer (Paper Analyzer Type SP-428, manufactured by Kawaguchi Denki K.K.) in the dark at 20° C., 65% RH and then allowed to stand for 10 seconds.
- the surface potential V 10 in this case was measured.
- the sample was allowed to stand for 60 seconds in the dark and then the potential V 70 was measured.
- the dark decay retention [DRR (%)] i.e., the percent retention of potential after decaying for 60 seconds in the dark, was calculated from the following formula:
- the surface of the photoconductive layer was charged to -400 volts by corona discharging, then irradiated by visible light at 2.0 lux. Then, the time required for decaying the surface potential V 10 to 1/10 thereof was measured, and the exposure amount E 1/10 (lux ⁇ sec) was calculated therefrom.
- the light-sensitive material was processed for plate-making by an automatic printing plate precursor ELP 404V (made by Fuji Photo Film Co., Ltd.) using ELP-T as a toner to form a toner image.
- ELP 404V made by Fuji Photo Film Co., Ltd.
- the composition was coated on a paper, which had been subjected to an electroconductive treatment, by a wire bar in a dry coating amount of 20 g/m 2 and dried for 1 minute at 110° C.
- the coated product was exposed by a high pressure mercury lamp for 3 minutes and allowed to stand in the dark for 24 hours under conditions of 20° C., 65% RH to obtain an electrophotographic light-sensitive material.
- the properties of the resulting light-sensitive material are shown in Table 8.
- Each of the light-sensitive materials of the present invention was excellent in the charging property, dark charge retentivity, and light-sensitivity and gave clear images having neither background fog nor fine line cutting even under severe conditions of high temperature and high humidity (30° C., 80% RH).
- the dispersion was coated on a paper, which had been subjected to an electroconductive treatment, by a wire bar in a dry coating amount of 18 g/m 2 and dried for 30 seconds at 110° C. and then heated for 2 hours at 120° C. Then, the coated product was allowed to stand for 24 hours under the conditions of 20° C., 65% RH to prepare an electrophotographic light-sensitive material.
- each light-sensitive material measured in the same manner as in Example 1 were excellent, and clear reproduced images having no background fog were obtained even under the high-temperature high-humidity condition (30° C., 80% RH). Also, when each light-sensitive material was used for printing as an offset master plate after processing, more than 8,000 prints having clear images could be obtained.
- a mixture of 6 g (as solid content) of the resin (A-7), 34 g (as solid content) of poly(ethyl methacrylate) (Mw 2.4 ⁇ 10 5 ; Resin (C-1)), 0.018 g of Cyanine Dye (I) having the following formula, 0.15 g of salicylic acid and 300 g of toluene was dispersed in a ball mill for 3 hours to prepare a coating composition for a photoconductive layer.
- the composition was coated on a paper, which had been subjected to an electroconductive treatment, by a wire bar in a dry coating amount of 20 g/m 2 and dried for 30 seconds at 110° C. Then, the coated product was allowed to stand for 24 hours in the dark under the conditions of 20° C., 65% RH to obtain each of the electrophotographic light-sensitive materials.
- An electrophotographic light-sensitive material was prepared in the same manner as Example 29, except that 34 g of the resin (D-1) having the following formula was used in place of 34 g of the resin (C-1). ##STR57##
- An electrophotographic light-sensitive material was prepared in the same manner as Example 29, except that 34 g of the resin (E-1) having the following formula was used in place of 34 g of the resin (C-1). ##STR58##
- An electrophotographic light-sensitive material was prepared in the same manner as Example 29, except that 6 g of the resin (R-1) having the following formula was used in place of 6 g of the binder resin (A-7) used in Example 29. ##STR59##
- An electrophotographic light-sensitive material was prepared in the same manner as Example 29, except that 6 g of the resin (R-2) having the following formula was used in place of 6 g of the binder resin (A-7) used in Example 29. ##STR60##
- Each of the electrophotographic light-sensitive materials was prepared in the same manner as Example 29, except that the following resins were used as a binder resin:
- the coating property surface smoothness
- electrostatic characteristics image forming performance under atmospheric condition
- image forming performance under the environmental condition 30° C., 80% RH were determined.
- each sample was used as an offset master plate after processing and the oil desensitizing property of the photoconductive layer (shown by the contact angle between oil desensitized photoconductive layer and water) and the printing properties (background stains, printing durability, etc.) were determined.
- the smoothness (sec/cc) of each light-sensitive material was measured using a Beck Smoothness Test Machine (manufactured by Kumagaya Riko K.K.) under an air volume of 1 cc.
- each light-sensitive material was repeatedly rubbed with emery paper (#1000) under a load of 60 g/cm 2 using a Heidon 14 Model surface testing machine (manufactured by Shinto Kagaku K.K.). After removing abrasion dusts from the layer, the film retention (%) was determined from the weight loss of the photoconductive layer, which was employed as the mechanical strength of the layer.
- Each light-sensitive material was charged by applying thereto corona discharging of -6 kV for 20 seconds using a paper analyzer (Paper Analyzer Type SP-428, manufactured by Kawaguchi Denki K.K.) in the dark at 20° C., 65% RH and then allowed to stand for 10 seconds.
- the surface potential V 10 in this case was measured.
- the sample was allowed to stand for 180 seconds in the dark and then the potential V 190 was measured.
- the dark decay retention [DRR (%)] i.e., the percent retention of potential after decaying for 180 seconds in the dark, was calculated from the following formula:
- the surface of the photoconductive layer was charged to -500 volts by corona discharging, then irradiated by monochromatic light of a wavelength of 785 n.m., the time required for decaying the surface potential V 10 to 1/10 thereof, and the exposure amount E 1/10 (erg/cm 2 ) was calculated therefrom.
- the surface of the photoconductive layer was charged to -500 volts by corona discharging, then irradiated by monochromatic light of a wavelength of 785 n.m., the time required for decaying the surface potential V 10 to 1/100 thereof, and the exposure amount E 1/100 (erg/cm 2 ) was calculated therefrom.
- Each light-sensitive material was allowed to stand a whole day and night under the environmental condition (I) of 20° C., 65% RH or the environmental condition (II) of 30° C., 80% RH. Then, each sample was charged to -5 kV, exposed by scanning with a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 785 n.m.) of 2.8 mW in output as a light source at an exposure amount on the surface of 50 erg/cm 2 , at a pitch of 25 ⁇ m, and a scanning speed of 330 m/sec., and developed using ELP-T (trade name, made by Fuji Photo Film Co., Ltd.) as a liquid developer followed by fixing. Then, the reproduced images (fog, image quality) were visually evaluated.
- ELP-T trade name, made by Fuji Photo Film Co., Ltd.
- Each light-sensitive material was passed once through an etching processor using a solution prepared by diluting an oil desensitizing solution ELP-EX (trade name, made by Fuji Photo Film Co., Ltd.) with two-fold volume of distilled water to oil desensitized the surface of the photoconductive layer. Then, one drop of distilled water (2 ⁇ l) was placed on the surface, and the contact angle between the surface and the water drop formed thereon was measured using a goniometer.
- ELP-EX oil desensitizing solution
- Each light-sensitive material was processed in the same manner as described in *4) to form a toner image, the sample was oil-desensitized under the same condition as in *5) described above, and the printing plate thus prepared was mounted on an offset printing machine (Oliver Model 52, manufactured by Sakurai Seisakusho K.K.) as an offset master plate following by printing. Then, the number of prints obtained without causing background stains on the non-image area of prints and problems on the quality of the image area was employed as the printing durability. The larger the number of prints, the higher the printing durability.
- the light-sensitive material of this invention was excellent in the smoothness of the photoconductive layer, the film strength, and electrostatic characteristics as well as the reproduced images formed by processing had no background stains and had clear image quality. This is assumed to be based on that the binder resin suitably adsorbed on the photoconductive particles and suitably covered the surface of the particles.
- the photoconductive layer was sufficiently oil-desensitized by an oil-desensitizing solution for the same reason as above and the contact angle between the non-image area and water was as low as below 10 degrees, which showed that the layer was sufficiently rendered hydrophilic. At printing, no background stain of prints was observed.
- each of the light-sensitive materials of Comparative Examples A-2 to F-2 show inferior electrostatic characteristics as compared with those of the light-sensitive materials of the present invention.
- E 1/100 values of Comparative Examples A-2 to F-2 are markedly higher than those of Examples.
- the E 1/100 value refers to the potential remaining in the non-image area (exposed area) after exposure in the image formation and, thus the lower the E 1/100 value, the lower the background stain in the non-image area after development.
- V R residual potential
- each of the light-sensitive materials of Comparative Examples A-2 to F-2 produced cutting of fine lines in the image area and background fog in the non-image area.
- the material was used as an offset master plate, the light-sensitive materials of Comparative Examples A-2 to F-2 produced fog from the beginning of the print due to the fog in the non-image area, even under the printing conditions where the light-sensitive material of Example 2 according to the present invention could provide 8,000 prints of good quality.
- Each of electrophotographic light-sensitive materials was prepared in the same manner as Example 29, except that 6.5 g of the resin (A) and 33.5 g of resin (C) shown in Table 11 below were used in place of the binder resin used in Example 29.
- the electrostatic characteristics and the printing property of the resulting light-sensitive material were measured in the same manner as Example 29. The results obtained are shown in Table 11 below.
- each of the plates provided more than 8,000 prints at printing.
- the light-sensitive material of the present invention is excellent in the smoothness of the photoconductive layer, film strength, electrophotographic properties and printing properties.
- An electrophotographic light-sensitive material was prepared in the same manner as Example 29, except that 6 g of the resin (A-21) and 34 g of the resin (D) shown in Table 12 below were used in place of the binder resin used in Example 29, and that 0.019 g of Dye (II) having the following formula was used in place of 0.02 g of the cyanine dye (I) used in Example 29. ##STR61##
- the light-sensitive material of the present invention was excellent in the electrostatic charging property, dark charge retentivity and photosensitivity, and provided clear reproduced images having no background fog even under high-temperature high-humidity condition (30° C., 80%RH). Also, when the light-sensitive material was used for printing as an offset master plate after processing, 9,000 to 10,000 prints of clear images having no background fog could be obtained.
- Each of the light-sensitive materials prepared above showed the following excellent properties even under severe conditions of high-temperature and high-humidity (30° C., 80% RH):
- V 10 -580 to -590 (V)
- the reproduced image showed a clear image having no background fog and no cutting of fine lines even under severe conditions of high-temperature and high-humidity (30° C., 80% RH). Further, when the light-sensitive material was used for printing as an offset master plate after processing, 10,000 prints of clear images having no background stain could be obtained.
- a mixture of 6 g of the resin (A-8), 34 g of the resin (D-1), 200 g of zinc oxide, 0.02 g of uranine, 0.04 g of Rose Bengal, 0.03 g of bromophenol blue, 0.20 g of phthalic anhydride and 300 g of toluene was dispersed in a ball mill for 4 hours.
- the dispersion was coated on a paper, which had been subjected to an electroconductive treatment, by a wire bar in a dry coating amount of 22 g/m 2 and dried for 1 minute at 110° C.
- the coated product was allowed to stand for 24 hours in the dark under conditions of 20° C., 65% RH to obtain an electrophotographic light-sensitive material.
- An electrophotographic light-sensitive material was prepared in the same manner as Example 63, except that 6 g of Resin (R-2) and 34 g of Resin (D-1) were used in place of the resin binder used in Example 63.
- Example 29 The above measurements were conducted by the same procedures as described in Example 29, except that the electrostatic characteristics and the image forming performance were determined in the following manner.
- the surface of the photoconductive layer was exposed to visible light of 2.0 lux, the time required for decaying the surface potential V 10 to 1/10 and 1/100 was determined, and the exposure amounts E 1/10 and E 1/100 (lux ⁇ sec), respectively, were calculated therefrom.
- Each of the light-sensitive materials was allowed to stand one day, and the material was processed by a full-automatic plate-making machine EPL-404V (trade name, made by Fuji Photo Film Co., Ltd.) using EPL-T (trade name, made by Fuji Photo Film Co., Ltd.) as a toner. Then, the reproduced image were visually evaluated for fog and image quality. In this case, the image formtion was conducted under the environmental condition (I) of 20° C., 65% RH and environmental condition (II) of 30° C., 80% RH.
- the original used for image formation also contained a cut-and-pasted up portion from a different original.
- Comparative Example G-2 showed particularly high exposure amount in E 1/100 , and this amount significantly increased at high temperature and high-humidity.
- the electrostatic characteristics of the light-sensitive material according to the present invention were found to be satisfactory.
- Comparative Example G-2 showed a frame of the cut-and-pasted up portion (i.e., edge marks of the cut-and-pasted up portions) as background stains in the non-image area, whereas, the light-sensitive material according to the present invention showed a clear image having no such background stains.
- the plate of the present invention provided 10,000 prints having a clear image free from background stains, whereas, in the plate produced from the light-sensitive material of Comparative Example G-2, the above edge marks in the cut-and-pasted up portion were not removed after oil-desensitizing treatment, and the marks were generated in prints from the beginning of the printing.
- Each of the light-sensitive materials was prepared in the same manner as Example 63, except that 6.5 g of the resin (A) and 33.5 g of the resin (C), (D) or (E) shown in Table 16 below were used in place of 6 g of the resin (A-8) and 34 g of the resin (D-1).
- the light-sensitive materials of this invention were excellent in the charging property, dark change retentivity, and light-sensitivity and provided clear images having neither background stains nor fine line cutting under severe conditions (30° C., 80% RH) at practical imaging.
- the dispersion was coated on a paper which had been subjected to an electroconductive treatment by a wire bar in a dry coating amount of 20 g/m 2 and dried for 1 minutes at 120° C. and then for 1.5 hours at 120° C. Then, the coated product was allowed to stand for 24 hours under the condition of 20° C., 65% RH to obtain an electrophotographic light-sensitive material.
- the resulting light-sensitive materials were evaluated for the electrostatic characteristics and the image forming performance and found to have satisfactory performance.
- an electrophotographic light-sensitive material having excellent electrostatic characteristics (in particular under severe conditions) and having clear images of good quality can be obtained.
- the light-sensitive material is useful for scanning exposure system using a semiconductor laser beam.
- the electrostatic characteristics can be further improved by using a repeating unit containing a specific methacrylate component represented by formula (Ia) or (Ib) in the resin (A) of the present invention.
- the mechanical strength of the electrophotographic light-sensitive material can be increased by incorporating heat- and/or photo-curable functional groups in the resin (A) of the present invention.
- the mechanical strength of the electrophotographic light-sensitive material can be increased by using a heat- and/or photo-curable resin and/or a crosslinking agent in combination with the resin (A).
- the mechanical strength of the electrophotographic light-sensitive material can be increased by using a specific resin having a weight average molecular weight of from 5 ⁇ 10 4 to 5 ⁇ 10 5 in combination with the resin (A).
Abstract
Description
TABLE A ______________________________________ Acidic Group in Resin (A) Acidic Group in Resin (E) ______________________________________ SO.sub.3 H and/or PO.sub.3 H.sub.2 COOH SO.sub.3 H, PO.sub.3 H.sub.2 and/or COOH ##STR27## ______________________________________
TABLE 1 __________________________________________________________________________ Resin (A) Monomer Chain Transfer Agent Polyfunctional Monomer __________________________________________________________________________ A-3 Methyl methacrylate (95 g) β-Mercaptopropionic acid (5 g) Divinylbenzene (2 g) A-4 Phenyl methacrylate (95 g) Thiomalic acid (5 g) " A-5 Ethyl methacrylate (95 g) Thiosalicylic acid (5 g) " A-6 2-Chlorophenyl methacrylate Thioglycolic acid (4 g) Ethylene glycol (96 g) dimethacrylate (2.5 g) A-7 2,6-Dichlorophenyl Thiosalicylic acid (3 g) Divinylbenzene (2.5 g) methacrylate (97 g) A-8 1-Naphthyl methacrylate 2-Mercaptoethylphosphonic acid Diethylene glycol (96 g) (4 g) diacrylate (2.8 g) A-9 2-Chloro-6-methylphenyl β-Mercaptopropionic acid (4 g) Trivinylbenzene (1.5 g) methacrylate (96 g) A-10 2-Bromophenyl methacrylate 2-(2-Mercaptoethyl)maleic acid Propylene glycol (94 g) anhydride (6 g) diacrylate (2.2 g) A-11 Methyl methacrylate (53 g) 2-(2-Mercaptoethylcarbamoyl)- Ethylene glycol Butyl methacrylate (40 g) propionic acid (7 g) diacrylate (2.0 g) A-12 Ethyl methacrylate (84 g) Thiosalicylic acid (6 g) Divinylbenzene (3 g) 2-Hydroxyethyl methacrylate (10 g) A-13 Benzyl methacrylate (87 g) Thioglycolic acid (5 g) Propylene glycol Glycidyl methacrylate (8 g) dimethacrylate (2.6 g) A-14 2-Chlorophenyl methacrylate β -Mercaptopropionic acid (4 g) Divinylbenzene (2 g) (88 g) 2,3-Dihydroxypropyl methacrylate (8 g) A-15 Phenyl methacrylate (87 g) 3-(2-Mercaptoethylcarbamoyl)- Divinylbenzene (2 g) 2-Isocyanatoethyl phthalic acid anhydride (8 g) methacrylate (5 g) A-16 Benzyl methacrylate (86 g) Thiomalic acid (4 g) Triethylene glycol 6-Hydroxyhexyl methacrylate diacrylate (1.8 g) (10 g) A-17 2-Acetylphenyl methacrylate 3-(2-Mercaptoethyloxycarbonyl)- Vinyl methacrylate (96 g) phthalic acid (4 g) (2.5 g) A-18 2-Naphthylmethyl Thiosalicylic acid (4 g) Divinylbenzene (2.2 g) methacrylate (96 g) A-19 2-Chlorophenyl methacrylate β-Mercaptopropionic acid (4 g) Ethylene glycol (86 g) dimethacrylate (2.6 g) Glycidyl methacrylate (10 g) A-20 Phenethyl methacrylate (95 g) β-Mercaptopropionic acid (5 g) Ethylene glycol dimethacrylate (2.8 g) A-21 2-Chlorophenyl methacrylate Thiosalicylic acid (6 g) Divinylbenzene (3 g) (84 g) Methyl acrylate (10 g) A-22 2-Acetylphenyl methacrylate Thioglycolic acid (5 g) Propylene glycol (95 g) dimethacrylate (2.6 g) A-23 2-Chlorophenyl methacrylate β-Mercaptopropionic acid (4 g) Divinylbenzene (2 g) (88 g) Glycidyl methacrylate (8 g) A-24 2-Chloro-6-methylphenyl 3-(2-Mercaptoethyloxy- Vinyl methacrylate methacrylate (96 g) carbonyl)phthalic acid (4 g) (2.5 g) A-25 2,6-Dichlorophenyl β-Mercaptopropionic acid (4 g) Ethylene glycol methacrylate (86 g) dimethacrylate (2.6 g) Ethyl methacrylate (10 g) __________________________________________________________________________
TABLE 2 __________________________________________________________________________ Comparative Comparative Comparative Example 1 Example 2 Example A-1 Example B-1 Example C-1 __________________________________________________________________________ Electrophotographic*.sup.1) Characteristics V.sub.10 (-V) I: (20° C., 65%) 510 590 450 450 450 II: (30° C., 80%) 505 575 410 430 425 DRR (%) (90 sec) I: (20° C., 65%) 75 85 75 80 78 II: (30° C., 80%) 70 83 70 75 75 E.sub.1/10 (erg/cm.sup.2) I: (20° C., 65%) 28 18 70 30 35 II: (30° C., 80%) 25 17 85 28 30 Image Forming*.sup.2) Performance I: (20° C., 65%) Good Excellent Background Dm lowered Dm lowered fog generated, Dm lowered II: (30° C., 80%) Good Excellent Background Dm lowered, Background fog generated densities of fog generated markedly fine lines markedly decreased __________________________________________________________________________
DRR (%)=(V.sub.100 /V.sub.10)×100
TABLE 3 ______________________________________ Comparison Example 3 Example D-1 ______________________________________ Smoothness of Photo-*.sup.3) 130 130 conductive Layer (sec/cc) Strength of Photo- 95 93 conductive Layer (%) Electrophotographic*.sup.4) Characteristics V.sub.10 (-V) I: (20° C., 65%) 570 445 II: (30° C., 80%) 555 430 DRR (%) I: (20° C., 65%) 83 70 II: (30° C., 80%) 80 65 E.sub.1/10 (erg/cm.sup.2) I: (20° C., 65%) 18 33 II: (30° C., 80%) 18 38 Image Forming*.sup.5) Performance I: (20° C., 65%) very Dm lowered, densities good of fine line and letter lowered II: (30° C., 80%) very Dm lowered, densities good of fine line and letter lowered, background stain generated slightly. Contact Angle*.sup.6) 10 or below 10 or below with Water (°C.) Printing Durability*.sup.7) 10,000 3,000 prints, cut of prints fine line and letter occurred ______________________________________
DRR (%)=(V.sub.130 /V.sub.10)×100
TABLE 4 ______________________________________ Smoothness of 135 (sec/cc) Photoconductive Layer Strength of 92 Photoconductive Layer (%) Electrophotographic Characteristics V.sub.10 (-V) I 565 (V) II 560 (V) D.R.R. (%) I 82% (120 sec value) II 80% E.sub.1/10 I 20 (erg/cm.sup.2) II 21 Image Forming I very good performance II very good Printing Durability 10,000 ______________________________________
TABLE 5 Electrostatic Characteristics (30° C., 80% RH) Example Resin (A) 10 g Resin (B) 30 g Crosslinking Agent V.sub.10 (-V) D.R.R. (%) E.sub.1/1 0 (erg/cm.sup.2) 5 A-2 ##STR39## --Mw38,000 1,3-xylylenedi-isocyanate 1.5 g 550 80 23 6 A-13 ##STR40## --Mw40,000 1,6-hexamethylene-diamine 1.3 g 550 78 26 7 A-6 ##STR41## --Mw41,000 Terephthalic acid 1.5 g 610 85 18 8 A-7 ##STR42## --Mw38,000 1,4-tetramethyl-enediamine 1.2 g 630 86 17 9 A-15 ##STR43## --Mw37,000 polyethyleneglycol 1.2 g 540 79 28 10 A-9 ##STR44## polypropyleneglycol 1.2 g 580 85 18 11 A-10 ##STR45## --Mw42,000 1,6-hexamethylene-diisocyanate 2 g 565 83 20 12 A-18 ##STR46## --Mw55,000 ethyleneglycol-dimethacrylate 2 g 560 84 20
TABLE 6 Example Resin (A) Resin (B) Group X Resin (B) Group Y 13 A-9 ##STR47## --Mw = 42,000 ##STR48## --Mw = 38,000 14 A-15 ##STR49## --Mw = 45,000 (B-10) 15 A-17 ##STR50## --Mw = 38,000 ##STR51## --Mw = 46,000 16 A-18 (B-10) ##STR52## --Mw = 33,000
______________________________________ V.sub.10 (V) D.R.R. (%) E.sub.1/10 (lux · sec) ______________________________________ I (20° C., 65% RH): -555 94 9.2 II (30° C., 80% RH): -545 93 9.5 ______________________________________
DRR (%)=(V.sub.70 /V.sub.10)×100
TABLE 7 __________________________________________________________________________ Example Resin (A) Resin (B) __________________________________________________________________________ 18 A-22 ##STR54## 19 A-23 ##STR55## __________________________________________________________________________
TABLE 8 ______________________________________ Ex- Surface Film E.sub.1/10 am- Smoothness Strength V.sub.10 D.R.R. (lux · Printing ple (cc/sec) (%) (-V) (%) sec) Durability ______________________________________ 18 125 97 565 93 10.5 9000 sheets 19 130 94 570 94 10.8 8500 sheets ______________________________________
TABLE 9 ______________________________________ Resin Resin Example (A) (B) Crosslinking Agent (Amount Added) ______________________________________ 20 A-1 B-1 Glutaconic acid (4 g) 21 A-2 B-2 1,3-Xylylene diisocyanate (3 g) 22 A-3 B-6 Ethylene glycol (1.5 g) 23 A-5 B-8 Ethylene glycol diacrylate (3 g) 24 A-11 B-3 Succinic acid (3.8 g) 25 A-12 B-1 None 26 A-16 B-11 None 27 A-20 B-8 1,6-Hexane diisocyanate 28 A-21 B-3 Gluconic acid (3.8 g) ______________________________________
TABLE 10 __________________________________________________________________________ Compar- Compar- Compar- Compar- Compar- Compara- Ex- Ex- Ex- ative ative ative ative ative ative am- am- am- Exam- Exam- Exam- Exam- Exam- Exam- ple 29 ple 30 ple 31 ple A-2 ple B-2 ple C-2 ple D-2 ple E-2 ple __________________________________________________________________________ F-2 Smoothness of Photo-*.sup.1) 135 140 140 130 135 135 135 140 140 conductive Layer (sec/cc) Strength of Photo-*.sup.2) 85 92 98 83 84 90 91 97 98 conductive Layer (%) Electrophotographic*.sup.3) Characteristics V.sub.10 (-V) I: (20° C., 65% RH) 610 600 680 430 480 435 450 460 485 II: (30° C., 80% RH) 590 580 660 380 430 380 400 435 455 DRR (%) I: (20° C., 65% RH) 78 80 85 60 69 60 72 64 75 II: (30° C., 80% RH) 75 77 80 52 60 51 67 53 68 E.sub.1/10 (erg/cm.sup.2) I: (20° C., 65% RH) 35 33 30 62 53 60 50 48 43 II: (30° C., 80% RH) 38 35 32 55 46 53 45 43 40 E.sub.1/100 (erg/cm.sup.2) I: (20° C., 65% RH) 46 44 41 108 84 93 80 90 72 II: (30° C., 80% RH) 53 47 45 115 88 90 78 88 67 Image Forming*.sup.4) Performance I: (20° C., 65% RH) good good good Dm low- Dm low- Dm low- Dm low- Dm lowered, Dm lowered, ered, back- ered, back- ered, back- ered, back- fine lines fine lines cut, ground ground ground ground stain background background stain stain stain slightly stain slightly stain slightly generated generated generated generated generated generated II: (30° C., 80% RH) good good good Dm low Dm low- Dm low- Dm lowered, Dm lowered, Dm lowered, ered, back- ered, back- ered, back- background background background ground ground ground stain stain stain stain stain stain generated, generated, generated, generated, generated, generated, fine lines fine lines fine lines fine line cut fine line cut find lines cut cut cut cut Contact Angle*.sup.5) 10 or 10 or 10 or 10 or less 10 or less 10 or less 10 or less 10 or less 10 or less with Water (°) less less less Printing Durability*.sup.6) 8,000 more more background background background background background background prints than than stain occur- stain occur- stain occur- stain occur- stain occur- stain occur- 10,000 10,000 red from red from red from red from the red from red from the prints prints the 1st the 1st the 1st 1st print 1st print 1st print print print print __________________________________________________________________________
DRR (%)=(V.sub.190 /V.sub.10)×100
TABLE 11 __________________________________________________________________________ Resin (B) Weight Average E.sub.1/10 E.sub.1/100 Resin (Weight Molecular V.sub.10 D.R.R. (erg/ (erg/ Example (A) No. Chemical Structure Ratio) Weight (-V) (%) cm.sup.2) cm.sup.2) __________________________________________________________________________ 32 A-2 C-2 Methyl methacrylate/ (60/40) 2.0 × 10.sup.5 535 76 40 57 Ethyl methacrylate 33 A-3 C-3 Methyl methacrylate/ (70/30 2.4 × 10.sup.5 510 72 43 58 Butyl methacrylate 34 A-4 C-4 Methyl methacrylate/ (80/20) 1.8 × 10.sup.5 540 79 38 51 Ethyl acrylate 35 A-5 C-5 Benzyl methacrylate (100) 3.6 × 10.sup.5 490 73 36 55 36 A-6 C-6 Phenyl methacrylate/ (80/20) 2.2 × 10.sup.5 590 85 39 50 Ethyl methacrylate 37 A-8 C-7 Styrene/Ethyl meth- (20/80) 1.8 × 10.sup.5 575 83 37 50 acrylate 38 A-10 C-8 Butyl methacrylate/ (85/15) 2.0 × 10.sup.5 570 83 38 51 2,2,2-Trifluoroethyl methacrylate 39 A-21 C-9 Vinyltoluene/Propyl (25/75) 1.5 × 10.sup.5 580 83 37 50 methacrylate 40 A-22 C-10 Styrene/Acrylo- (20/15/65) 1.8 × 10.sup.5 560 82 38 51 nitrile/Butyl acrylate __________________________________________________________________________ (The electrostatic characteristics were measured under the condition of 30° C., 80% RH.)
TABLE 12 __________________________________________________________________________ Weight Average Resin D R X a/b(*) Molecular Weight __________________________________________________________________________ D-2 C.sub.2 H.sub.5 ##STR62## 96/4 12 × 10.sup.4 D-3 " ##STR63## 95/5 9.5 × 10.sup.4 D-4 C.sub.4 H.sub.9 ##STR64## 98/2 10 × 10.sup.4 D-5 " ##STR65## 97/3 11.5 × 10.sup.4 D-6 " ##STR66## 96/4 20 × 10.sup.4 D-7 C.sub.2 H.sub.5 ##STR67## 95/5 8.8 × 10.sup.4 D-8 C.sub.3 H.sub.7 ##STR68## 95/5 9.5 × 10.sup.4 D-9 C.sub.4 H.sub.9 ##STR69## 96/4 10.5 × 1O.sup.4 D-10 C.sub.2 H.sub.5 ##STR70## 97/3 10.5 × 10.sup. 4 D-11 C.sub.4 H.sub.9 ##STR71## 95/5 13 × 10.sup.4 __________________________________________________________________________ *weight ratio
TABLE 13 __________________________________________________________________________ Image Forming Printing V.sub.10 E.sub.1/10 Performance Durability Example Resin (D) (-V) D.R.R. (erg/cm.sup.2) (30° C., 80% RH) (Sheets) __________________________________________________________________________ 41 D-2 570 84 48 Good 9000 42 D-3 575 86 46 " " 43 D-4 550 80 49 " 10000 44 D-5 565 82 50 " " 45 D-6 550 80 44 " 9000 46 D-7 545 78 48 " " 47 D-8 555 79 46 " " 48 D-9 540 78 45 " " 49 D-10 545 78 43 " " 50 D-11 540 77 43 " " __________________________________________________________________________ (The electrostatic characteristics were determined under the condition of 30° C., 80% RH.)
TABLE 14 __________________________________________________________________________ Weight Average Example Resin (E) R X x/y (*) Molecular __________________________________________________________________________ Weight 51 E-2 C.sub.2 H.sub.5 ##STR73## 99.5/0.5 1.8 × 10.sup.5 52 E-3 " ##STR74## 99.5/0.5 2.0 × 10.sup.5 53 E-4 " ##STR75## 99.2/0.8 2.1 × 10.sup.5 54 E-5 C.sub.4 H.sub.9 ##STR76## 99.7/0.3 2.5 × 10.sup.5 55 E-6 C.sub.4 H.sub.9 ##STR77## 99.7/0.3 1.5 × 10.sup.5 56 E-7 C.sub.2 H.sub.5 ##STR78## 99.5/0.5 1.1 × 10.sup.5 57 E-8 CH.sub.2 C.sub.6 H.sub.5 ##STR79## 99.4/0.6 2.1 × 10.sup.5 58 E-9 C.sub.3 H.sub.7 ##STR80## 99.7/0.3 2.2 × 10.sup.5 59 E-10 C.sub.4 H.sub.9 ##STR81## 99.5/0.5 2.0 × 10.sup.5 60 E-11 C.sub.3 H.sub.7 ##STR82## 99.7/0.3 2.1 × 10.sup.5 61 E-12 C.sub.2 H.sub.5 ##STR83## 99.7/0.3 1.6 × 10.sup.5 62 E-13 C.sub.2 H.sub.5 ##STR84## 99.4/0.6 2.2 × 10.sup.5 __________________________________________________________________________ (*) Weight Ratio
TABLE 15 ______________________________________ Comparative Example 63 Example G-2 ______________________________________ Binder Resin (A-2)/(C-2) (R-2)/(D-1) Smoothness of Photo- 145 140 conductive Layer (sec/cc) Strength of Photo- 98 97 conductive Layer (%) Electrostatic Characteristics*.sup.8) V.sub.10 (-V) I (20° C., 65% RH) 565 540 II (30° C., 80% RH) 560 530 D.R.R. (%) I (20° C., 65% RH) 96 90 II (30° C., 80% RH) 94 86 E.sub.1/10 (lux · sec) I (20° C., 65% RH) 9.3 13.0 II (30° C., 80% RH) 10.3 17.5 E.sub.1/100 (lux · sec) I (20° C., 65% RH) 28 48 II (30° C., 80% RH) 30 53 Imaging Forming Performance*.sup.8) I (20° C., 65% RH) good edge marks of pasted-up portion appeared II (30° C., 80% RH) good edge marks of pasted-up portion appeared significantly Contact Angle 10 or less 10 or less with Water (°) Printing Durability 10,000 Edge marks of pasted- prints up portion appeared as background stains from the beginning of printing ______________________________________
TABLE 16 ______________________________________ Example Resin (A) Resin (C), (D) or (E) ______________________________________ 64 A-1 C-2 65 A-4 C-7 66 A-5 C-10 67 A-7 D-2 68 A-8 D-4 69 A-10 D-6 70 A-11 D-7 71 A-21 D-9 72 A-24 D-10 73 A-25 D-11 74 A-2 E-4 75 A-25 E-5 76 A-6 E-6 77 A-7 E-9 78 A-8 E-11 79 A-3 E-12 80 A-11 E-8 81 A-20 E-10 ______________________________________
Claims (13)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28202989A JPH03144571A (en) | 1989-10-31 | 1989-10-31 | Electrophotographic sensitive body |
JP1-282029 | 1989-10-31 | ||
JP2-13739 | 1990-01-25 | ||
JP02013739A JP3096706B2 (en) | 1990-01-25 | 1990-01-25 | Electrophotographic photoreceptor |
Publications (1)
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US5147752A true US5147752A (en) | 1992-09-15 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US07/607,328 Expired - Lifetime US5147752A (en) | 1989-10-31 | 1990-10-30 | Process for producing electrophotographic light-sensitive material |
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US (1) | US5147752A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5601958A (en) * | 1994-04-08 | 1997-02-11 | Fuji Photo Film Co., Ltd. | Method for preparation of printing plate by electrophotographic process |
US6261700B1 (en) * | 1998-12-30 | 2001-07-17 | 3M Innovative Properties Co | Ceramer containing a brominated polymer and inorganic oxide particles |
US20060153057A1 (en) * | 2005-01-07 | 2006-07-13 | Lintec Corporation | Protective film for optical disks and optical disk using the same |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4952475A (en) * | 1988-02-09 | 1990-08-28 | Fuji Photo Film Co., Ltd. | Electrophotographic photoreceptor comprising binder resin containing terminal acidic groups |
US4968572A (en) * | 1987-09-11 | 1990-11-06 | Fuji Photo Film Co., Ltd. | Electrophotographic photoreceptor with binder having terminal acidic group |
US5009975A (en) * | 1988-10-04 | 1991-04-23 | Fuji Photo Film Co., Ltd. | Electrophotographic photoreceptor |
-
1990
- 1990-10-30 US US07/607,328 patent/US5147752A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4968572A (en) * | 1987-09-11 | 1990-11-06 | Fuji Photo Film Co., Ltd. | Electrophotographic photoreceptor with binder having terminal acidic group |
US4952475A (en) * | 1988-02-09 | 1990-08-28 | Fuji Photo Film Co., Ltd. | Electrophotographic photoreceptor comprising binder resin containing terminal acidic groups |
US5009975A (en) * | 1988-10-04 | 1991-04-23 | Fuji Photo Film Co., Ltd. | Electrophotographic photoreceptor |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5601958A (en) * | 1994-04-08 | 1997-02-11 | Fuji Photo Film Co., Ltd. | Method for preparation of printing plate by electrophotographic process |
US6261700B1 (en) * | 1998-12-30 | 2001-07-17 | 3M Innovative Properties Co | Ceramer containing a brominated polymer and inorganic oxide particles |
US20060153057A1 (en) * | 2005-01-07 | 2006-07-13 | Lintec Corporation | Protective film for optical disks and optical disk using the same |
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